Fungicidal combinations of active substances

ABSTRACT

The present invention relates to fungicidally active compound combinations of a fluorobenzothiazole derivative of the formula (I)  
                 
and at least one of the compounds listed in the disclosure.

The present invention relates to novel active compound combinationswhich consist of a known fluoro-benzothiazole derivative and furtherknown fungicidally active compounds, and which are highly suitable forcontrolling phytopathogenic fungi.

It is already known that isopropyl1-({[1-(6-fluoro-1,3-benzothiazol-2-yl)ethyl]-amino}carbonyl)-2-methylpropylcarbamatehas fungicidal properties (cf. EP-A1-775 696). The activity of thiscompound is good; however, at low application rates it is in some casesnot satisfactory.

Furthermore, it is already known that a large number of triazolederivatives, aniline derivatives, dicarboximides and other heterocyclescan be employed for controlling fungi (cf. EP-A 0 040 345, DE-A 22 01063, DE-A 23 24 010, Pesticide Manual, 9th Edition (1991), pages 249 and827, EP-A 0 382 375 and EP-A 0 515 901). Likewise, the activity of thesecompounds is not always satisfactory at low application rates.

Finally, it is also known that1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidineimine can beused for controlling animal pests such as insects (cf. Pesticide Manual,9th Edition (1991), page 491). However, fungicidal properties havehitherto not been described for this compound.

Furthermore, it is already known that1-(3,5-dimethyl-isoxazol-4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazolehas fungicidal properties (cf. WO 97-06171).

Furthermore, it is already known that substituted azodioxacycloalkeneshave fungicidal properties (cf. EP-B-712 396).

Finally, it is also known that substituted halogenopyrimidines havefungicidal properties (cf. DE-A1-196 46 407, EP-B-712 396).

It has now been found that the novel active compound combinationscomprising a fluorobenzothiazole derivative of the formula

and

-   (1) a triazole derivative of the formula    -   in which    -   X represents chlorine or phenyl and    -   Y represents        and/or-   (2) the triazole derivative of the formula    and/or-   (3) an aniline derivative of the formula    -   in which    -   R¹ represents hydrogen or methyl,        and/or-   (4)    N-[1-(4-chloro-phenyl)-ethyl]-2,2-dichloro-1-ethyl-3-methyl-cyclopropane-carboxamide    of the formula    and/or-   (5) the zinc propylene-1,2-bis-(dithiocarbamidate) of the formula    and/or-   (6) at least one thiocarbamate of the formula    -   Me=Zn or Mn or a mixture of Zn and Mn        and/or-   (7) the aniline derivative of the formula    and/or-   (8) the compound of the formula    and/or-   (9) the benzothiadiazole derivative of the formula    and/or-   (10) the    8-t-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxaspiro[5,4]-decane    of the formula    and/or-   (11) the compound of the formula    and/or-   (12) the compound of the formula    and/or-   (13) the compound of the formula    and/or-   (14) the cyanoxime derivative of the formula    and/or-   (15) a pyrimidine derivative of the formula    -   in which    -   R² represents methyl, —C≡C—CH₃ (mepanipyrim) or cyclopropyl        (cyprodinyl),        and/or-   (16) an aniline derivative of the formula    and/or-   (17) the morpholine derivative of the formula    and/or-   (18) the phthalimide derivative of the formula    and/or-   (19) the phosphorus compound of the formula    and/or-   (20) the hydroxyethyl-triazole derivative of the formula    and/or-   (21) the    1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine of the    formula    and/or-   (22) the oxazolidinedione of the formula    and/or-   (23) the benzamide derivative of the formula    and/or-   (24) a guanidine derivative of the formula    -   in which    -   m represents integers from 0 to 5 and    -   R³ represents hydrogen (17 to 23%) or the radical of the formula        and/or-   (25) the triazole derivative of the formula    and/or-   (26) the halogeno-benzimidazole of the formula    and/or-   (27) the halogenopyrimidine of the formula    and/or-   (28) the tetrachloro-isophthalo-dinitrile of the formula    and/or-   (29) the compound of the formula    and/or-   (30) the pyridineamine of the formula    and/or-   (31) the thiazolecarboxamide of the formula    and/or-   (32) the sulphonamide of the formula    and/or-   (33) the compound of the formula    and/or-   (34) the compound of the formula    and/or-   (35) the compound of the formula    and/or-   (36) the diamide of the formula    and/or-   (37) the methoxyacrylate derivative of the formula    and/or-   (38) the quinoline derivative of the formula    and/or-   (39) the phenylamide derivative of the formula    and/or-   (40) the phenylamide derivative of the formula    and/or-   (41) the dicarboxime derivative of the formula    and/or-   (42) the phosphonic acid of the formula    and/or-   (43) the pyrrole derivative of the formula    and/or-   (44) the phenyl carbonate of the formula    and/or-   (45) the copper compounds    a) copper oxychloride (XXXXVIa)    b) copper hydroxid (XXXXVIb)    and/or-   (46) the imidazole derivative of the formula    and/or-   (47) the triazole derivative of the formula-   a)    and/or-   b)    and/or-   c)    and/or-   d)    and/or-   e)    and/or-   f)    and/or-   g)

and/or

-   h)    and/or-   (48) a compound of the general formula    -   in which    -   R¹ represents unsubstituted or fluorine-, chlorine-, bromine-,        methyl- or ethyl-substituted phenyl, 2-naphthyl,        1,2,3,4-tetrahydronaphthyl or indanyl,        and/or-   (49)    N-methyl-2-(methoxyimino)-2-[2-([1-(3-tri-fluoro-methyl-phenyl)ethoxy]iminomethyl)phenyl]acetamide    of the formula    and/or-   (50)    2,4-dihydro-5-methoxy-2-methyl-4-[2-([([1-(3-tri-fluoro-methylphenyl)ethylidene]amino)oxy]methyl)phenyl]-3H-1,2,4-triazol-3-one    of the formula    and/or-   (51) the compound of the formula    have very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compoundcombinations according to the invention is considerably higher than thesum of the activities of the individual active compounds. Thus, anunforeseeable, true synergistic effect is present, and not just anaddition of activities.

From the structural formula of the active compound of the formula (I),it can be seen that the compound has two asymmetrically substitutedcarbon atoms. Accordingly, the product can be present as a mixture ofdifferent isomers or else in the form of a single isomer.

Preferred compounds of the formula (I) are compounds in which the aminoacid moiety is formed from i-propyloxycarbonyl-L-valine and thefluoro-benzothiazoleethylamine moiety is racemic, but has, inparticular, the (R) configuration.

The formula (II) includes the compounds

-   1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one    of the formula-   1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol    of the formula    and-   1-(4-phenyl-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol    of the formula

The formula (IV) includes the aniline derivatives of the formulae

and

It is evident from the structural formula for the active compound of theformula (V) that the compound has three asymmetrically substitutedcarbon atoms. The product may therefore be present as a mixture ofdifferent isomers, or else in the form of a single component. Particularpreference is given to the compounds

-   N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1S)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide    of the formula    and-   N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1R)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide    of the formula

The formula (VII) includes the compounds

(VIIa) Me=Zn (zineb),

(VIIb) Me=Mn (maneb) and

(VIIc) mixture of (VIIa) and (VIIb) (mancozeb).

The formula (XVI) includes the compounds

The compound of the formula (XVII) can be present as methylN-(2,6-dimethylphenyl)-N-(methoxyacetyl)-DL-alaninate (metalaxyl, XVIIa)or as methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate(metalaxyl-M, XVIIb).

The hydroxyethyl-triazole derivative of the formula (XXI) can be presentin the “thiono” form of the formula

or in the tautomeric “mercapto” form of the formula

For simplicity's sake, only the “thiono” form is given in each case.

The guanidine derivative of the formula (XXV) is a substance mixturewith the common name guazatine.

From the structural formula for the active compouds of the formula(XXXXIX), it can be seen that the compounds can be present as E or Zisomers. Accordingly, the product can be present as a mixture ofdifferent isomers or else in the form of a single isomer. Preference isgiven to compounds of the formula (XXXXIX) in which the compounds of theformula (XXXXIX) are present as E isomer. Particular preference is givento the compounds of the formulae

and their isomers.

The following active compounds are particularly preferred mixingpartners of the compounds of the formula (I):

(3) tolylfluanid (IVb),

(5) propineb (VI),

(6) mancozeb (VIIc),

(7) fenhexamid (VI),

(8) iprovalicarb (VIII),

(11) azoxystrobin (XII),

(12) trifloxystrobin (XIII),

(13) compound of the formula (XIV),

(18) folpet (XIX),

(20) compound of the formula (XXI),

(26) compound of the formula (XXVII),

(27) compound of the formula (XXVIII),

(28) chlorothalonil (XXIX),

(30) fluazinam (XXXI), and

(45) copper compounds

a) copper oxychloride (XXXXVIa)

b) copper hydroxide (XXXXVIb).

The components which are present in the active combinations according tothe invention in addition to a halogeno-benzimidazole of the formula(XXVII) are also known.

Specifically, the active compounds are described in the followingpublications:

(1) compounds of the formula (H)

DE-A 22 01 063

DE-A 23 24 010

(2) compound of the formula (III)

EP-A 0 040 345

(3) compounds of the formula (IV)

Pesticide Manual, 9th Ed. (1991), pages 249 and 827

(4) compound of the formula (V) and individual derivatives thereof.

EP-A 0 341 475

(5) compound of the formula (VI)

Pesticide Manual, 9th Ed. (1991), page 726

(6) compounds of the formula (VII)

Pesticide Manual, 9th Ed. (1991), pages 529, 531 and 866

(7) compound of the formula (VIII)

EP-A 0 339 418

(8) compound of the formula (IX)

EP-A 0 472 996

(9) compound of the formula (X)

EP-A 0 313 512

(10) compound of the formula (XI)

EP-A 0 281 842

(11) compound of the formula (XII)

EP-A 0 382 375

(12) compound of the formula (XIII)

EP-A460 575

(13) compound of the formula (XIV)

DE-A 196 02 095

(14) compound of the formula (XV)

Pesticide Manual, 9th Ed. (1991), page 206

(15) compounds of the formula (XVI)

EP-A 0 270 111

EP-A 0 310 550

(16) compound of the formula (XVII)

Pesticide Manual, 9th Ed. (1991), page 554

(17) compound of the formula (XVIII)

EP-A0219 756

(18) compound of the formula (XIX)

Pesticide Manual, 9th Ed. (1991), page 431

(19) compound of the formula (XX)

Pesticide Manual, 9th Ed. (1991), page 443

(20) compound of the formula (XXI)

WO 96-16048

(21) compound of the formula (XXII)

Pesticide Manual, 9th Ed. (1991), page 491

(22) compound of the formula (XXII)

EP-A 0 393 911

(23) compound of the formula (XXIV)

EP-A 0 600 629

(24) substance of the formula (XXV)

Pesticide Manual, 9th Ed. (1991), page 461

(25) compound of the formula (XXVI)

Pesticide Manual, 9th Ed. (1991), page 654

(26) compound of the formula (XXVII)

WO 97-06171

(27) compound of the formula (XXVIII)

DE-A1-196 46 407, EP-B-0 712 396

(28) compound of the formula (XXIX)

U.S. Pat. No. 3,290,353

(29) compound of the formula (XXX)

DE-A-156 7169

(30) compound of the formula (XXXI)

EP-A-0 031 257

(31) compound of the formula (XXXII)

EP-A-0 639 547

(32) compound of the formula (XXXI)

EP-A-0 298 196

(33) compound of the formula (XXXIV)

EP-A-600 629

(34) compound of the formula (XXXV)

DE-A-2 149 923

(35) compound of the formula (XXXVI)

DE-A-2 012 656

(36) compound of the formula (XXXVII)

U.S. Pat. No. 1,972,961

(37) compound of the formula (XXXVIII)

EP-A-326 330

(38) compound of the formula (XXXI)

EP-A 278 595

(39) compound of the formula (XXXX)

DE-A-3 030 026

(40) compound of the formula (XXXXI)

DE-A-2 903 612

(41) compound of the formula (XXXXII)

U.S. Pat. No. 2,553,770

(42) compound of the formula (XXXXIII)

known and commercially available

(43) compound of the formula (XXXXIV)

EP-A-206 999

(44) compound of the formula (XXXXV)

EP-A-78 663

(45) a) compound of the formula (XXXXVIa)

-   -   known and commercially available

b) compound of the formula (XXXXVIb)

-   -   known and commercially available        (46) compound of the formula (XXXXVII)

DE-A-2 429 523

(47) a) compound of the formula (XXXXVIa)

-   -   EP-A-112 284

b) compound of the formula (XXXXVIIIb)

-   -   DE-A-3 042 303

c) compound of the formula (XXXXVIIIc)

-   -   DE-A-3 406 993

d) compound of the formula (XXXXVIIId)

-   -   EP-A-68 813

e) compound of the formula (XXXXVIIIe)

-   -   DE-A-2551560

f) compound of the formula (XXXXVIIIf)

-   -   EP-A-145 294

g) compound of the formula (XXXXVIIIg)

-   -   DE-A-3 721 786

h) compound of the formula (XXXXVIIIh)

-   -   EP-A-234 242        (48) compound of the formula (XXXXIX)

WO 96/23763

(49) compound of the formula (XXXXX)

-   -   EP-A-596 254        (50) compound of the formula (XXXXXI)

WO 98/23155

(50) compound of the formula (XXXXXII)

EP-A-569 384.

In addition to an active compound of the formula (I), the activecompound combinations according to the invention comprise at least oneactive compound of the compounds of groups (1) to (51). Additionally,they may comprise further fungicidally active additives.

The synergistic effect is particularly pronounced when the activecompounds in the active compound combinations according to the inventionare present in certain weight ratios. However, the weight ratios of theactive compounds in the active compound combinations can be variedwithin a relatively wide range. In general,

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (1),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (2),

from 1 to 150 parts by weight, preferably from 1 to 100 parts by weight,of active compound of group (3),

from 0.1 to 10 parts by weight, preferably from 0.2 to 5 parts byweight, of active compound of group (4),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (5),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (6),

from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight,of active compound of group (7),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (8),

from 0.02 to 50 parts by weight, preferably from 0.1 to 10 parts byweight, of active compound of group (9),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (10),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (11),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (12),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (13),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (14),

from 0.2 to 50 parts by weight, preferably from 1 to 20 parts by weight,of active compound of group (15),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (16),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (17),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (18),

from 0.1 to 150 parts by weight, preferably from 1 to 100 parts byweight, of active compound of group (19),

from 0.02 to 50 parts by weight, preferably from 0.2 to 10 parts byweight, of active compound of group (20),

from 0.05 to 20 parts by weight, preferably from 0.1 to 10 parts byweight, of active compound of group (21),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (22),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (23),

from 0.01 to 150 parts by weight, preferably from 1 to 100 parts byweight, of active compound of group (24),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (25),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (26),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (27),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (28),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (29),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (30),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (31),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (32),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (33),

from 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, ofactive compound of group (34),

from 0.1 to 50 parts by weight, preferably from 1 to 10 parts by weight,of active compound of group (35),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (36),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (37).

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (38),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (39),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (40),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (41),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (42),

from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight,of active compound of group (43),

from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight,of active compound of group (44),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (45a),

from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight,of active compound of group (45b),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (46),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47a),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47b),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47c),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47d),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47e),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47f),

from 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (47g),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (47h),

from 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (48),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (49),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (50),

from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts byweight, of active compound of group (51)

are present per part by weight of active compound of the formula (I).

The active compound combinations according to the invention have verygood fungicidal properties and can be employed for controllingphytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes,Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Deuteromycetes, etc.

The active compound combinations according to the invention areparticularly suitable for controlling Phytophthora infestans andPlasmopara viticola.

The fact that the active compound combinations are well tolerated byplants at the concentrations required for controlling plant diseasespermits the treatment of above-ground parts of plants, of propagationstock and seeds, and of the soil. The active compound combinationsaccording to the invention can be employed for foliar application orelse as seed dressings.

The active compound combinations according to the invention may also beemployed to increase the yield of crops. However, they have reducedtoxicity and are tolerated well by plants.

According to the invention, it is possible to treat all plants and partsof plants. Plants are to be understood here as meaning all plants andplant populations such as desired and undesired wild plants or cropplants (including naturally occurring crop plants). Crop plants can beplants which can be obtained by conventional breeding and optimizationmethods or by biotechnological and genetic engineering methods orcombinations of these methods, including the transgenic plants andincluding plant cultivars which can or cannot be protected by plantbreeders certificates. Parts of plants are to be understood as meaningall above-ground and below-ground parts and organs of plants, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seedsand also roots, tubers and rhizomes. Parts of plants also includeharvested plants and vegetative and generative propagation material, forexample seedlings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and parts of plants according to theinvention with the active compounds is carried out directly or by actionon their environment, habitat or storage area according to customarytreatment methods, for example by dipping, spraying, evaporating,atomizing, broadcasting, brushing-on and, in the case of propagationmaterial, in particular in the case of seeds, furthermore by one- ormulti-layer coating.

The active compound combinations according to the invention can beconverted to the customary formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols andmicroencapsulations in polymeric substances and in coating compositionsfor seeds, and ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds or active compound combinations with extenders,that is liquid solvents, liquefied gases under pressure, and/or solidcarriers, optionally with the use of surfactants, that is emulsifiersand/or dispersants, and/or foam formers. If the extender used is water,it is also possible to use, for example, organic solvents as auxiliarysolvents. Essentially, suitable liquid solvents include: aromatics suchas xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water. Liquefied gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at ambienttemperature and under atmospheric pressure, for example aerosolpropellants such as butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks. Suitableemulsifiers and/or foam formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates, or else proteinhydrolysates. Suitable dispersants are: for example lignin-sulphitewaste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compounds, preferably between 0.5 and 90%.

The active compound combinations according to the invention, as such orin their formulations, can also be applied in a mixture with knownfungicides, bactericides, acaricides, nematicides or insecticides, tobroaden the activity spectrum or to prevent the development ofresistance, for example. In many cases, synergistic effects areobtained, i.e. the activity of the mixture is greater than the activityof the individual components.

A mixture with other known active compounds such as herbicides or withfertilizers and growth regulators is also possible.

The active compound combinations can be used as such, in the form oftheir formulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, spreading, and as a powder for dry seedtreatment, a solution for seed treatment, a water-soluble powder forseed treatment, a water-soluble powder for slurry treatment, or byencrusting.

When using the active compound combinations according to the invention,the application rates can be varied within a relatively wide range,depending on the kind of application. In the treatment of parts ofplants, the application rates of the active compound combination aregenerally between 0.1 and 10,000 g/ha, preferably between 10 and 1000g/ha. In the treatment of seeds, the application rates of the activecompound combination are generally between 0.001 and 50 g per kilogramof seed, preferably between 0.01 and 10 g per kilogram of seed. In thetreatment of the soil, the application rates of the active compoundcombination are generally between 0.1 and 10,000 g/ha, preferablybetween 1 and 5000 g/ha.

The good fungicidal activity of the active compound combinationsaccording to the invention is evident from the examples below. While theindividual active compounds exhibit weaknesses with regard to thefungicidal activity, the combinations have an activity which exceeds thesum of individual activities.

A synergistic effect of fungicides is always present when the fungicidalactivity of the active compound combinations exceeds the total of theactivities of the active compounds when applied individually.

The expected activity for a given combination of two active compoundscan be calculated as follows (cf. Colby, S. R., “Calculating Synergisticand Antagonistic Responses of Herbicide Combinations”, Weeds 15, (1967),20-22):

If

X is the efficacy when applying active compound A at an application rateof m g/ha,

Y is the efficacy when applying active compound B at an application rateof n g/ha and

E is the efficacy when applying the active compounds A and B at anapplication rate of m and n g/ha,

then $E = {X + Y - \frac{X \cdot Y}{100}}$

The efficacy is calculated in %. 0% is an efficacy which corresponds tothat of the control, whereas an efficacy of 100% means that no infectionis observed.

If the actual fungicidal activity exceeds the calculated value, then theactivity of the combination is superadditive, i.e. a synergistic effectexists. In this case, the efficacy which was actually observed must begreater than the value for the expected efficacy (E) calculated from theabovementioned formula.

The examples that follow illustrate the invention. However, theinvention is not limited to the examples.

EXAMPLE 1

Phytophthora Test (Tomato)/Protective Solvent: 47 parts by weight ofacetone Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration, or a commercial formulation ofactive compound or active compound combination is diluted with water tothe desired concentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. The plants are then placedin an incubation cabin at about 20° C. and 100% relative atmospherichumidity.

Evaluation is carried out 3 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

The activity found for the active compound combination according to theinvention is greater than the calculated activity, i.e. there is asynergistic effect. At a mixing ratio of 1:1 and an application rate of0.1 g/ha, the combination of the compound of the formula (1) and thehalogeno-benzimidazole of the formula No. XXVII has an actual efficacyof 73%. At 63%, the expected value, calculated using Colby's formula, isconsiderably lower.

Active compounds, application rates and test results are shown in thetables below. TABLE 1 Phytophthora test (tomato)/protective Activecompound Effi- Active compound application cacy known: rate in g/ha in %compound of the formula (XXVII) 0.1 30

compound of the formula (I) 0.1 47

Mixture according to the invention: Active compound Expected value,Mixing application Actual calculated using Active compound ratio rate ing/ha efficacy Colby's formula XXVII 0.1 63 + {close oversize brace}1:1 + {close oversize brace} 73 I 0.1

TABLE 2 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

propineb (VI) 20 19 (VI)

Mixture according to the invention Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 57 + {close oversize brace} 1:20 + {close oversizebrace} 94 propineb (VI) 20

TABLE 3 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

chlorothalonil (XXIX) 20 12

Mixture according to the invention Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 1 53 + + {close oversize brace} 84 chlorothalonil{close oversize brace} 1:20 20 (XXIX)

TABLE 4 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

dichlofluanid (IVa) 20  5

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 50 + + {close oversize brace} 87 dichlofluanid{close oversize brace} 1:20 20 (IVa)

TABLE 5 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

tolylfluanid (IVb) 20 21

Mixture according to the invention: Active Expected compound valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 58 + + {close oversize brace} 95 tolyifluanid{close oversize brace} 1:20 20 (IVa)

TABLE 6 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

folpet (XIX) 20  0

Mixture according to the invention: Active Expected compound valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 47 + {close oversize brace} 1:20 + {close oversizebrace} 95 folpet (XIX) 20

TABLE 7 Phytophthora test tomato/protective Active compound Effi- Activecompound application cacy known: rate in g/ha in % compound of theformula (I)  1 39

mancozeb (VIIc) 20 28 Mixture according to the invention: ExpectedActive value calcu- compound lated using application Actual Colby'sMixing ratio rate in g/ha efficacy formula (I) 1 56 + {close oversizebrace} 1:20 + {close oversize brace} 68 mancozeb (VIIc) 20

TABLE 8 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

bitertanol (IIc) 10  4 Mixture according to the invention: Activecompound Expected value application Actual calculated using Mixing ratiorate in g/ha efficacy Colby's formula (I) 1 1 49 + {close oversizebrace} 1:10 + {close oversize brace} 73 bitertanol (IIc) 10

TABLE 9 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

tebuconazole (III) 10  5

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 50 + + {close oversize brace} 73 tebuconazole{close oversize brace} 1:10 10 (III)

TABLE 10 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

triadimenol (IIb) 10  0 Mixture according to the invention: Activecompound Expected value application Actual calculated using Mixing ratiorate in g/ha efficacy Colby's formula (I) 1 47 + + {close oversizebrace} 88 triadimenol {close oversize brace} 1:10 10 (IIb)

TABLE 11 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

imidacloprid (XXII) 10  0

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 47 + + {close oversize brace} 71 imidacloprid{close oversize brace} 1:10 10 (XXII)

TABLE 12 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

compound of the formula (XXI) (20) 10  2 (XXI)

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 48 + {close oversize brace} 1:10 + {close oversizebrace} 62 (XXI) (20) 10

TABLE 13 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

fenhexamid (VIII) 10 13

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 54 + + {close oversize brace} 70 fenhexamid {closeoversize brace} 1:10 10 (VIII)

TABLE 14 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

carpropamid (V) 10  0

Mixture according to the invention: Active Expected value compoundcalculated application Actual using Colby's Mixing ratio rate in g/haefficacy formula (I) 1 47 + {close oversize brace} 1:10 + {closeoversize brace} 90 carpropamid (V) 10

TABLE 15 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 47

spiroxamine (XI) 10  0

Mixture according to the invention: Active Expected value compoundcalculated application Actual using Colby's Mixing ratio rate in g/haefficacy formula (I) 1 47 + {close oversize brace} 1:10 + {closeoversize brace} 86 spiroxamine (XI) 10

TABLE 16 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I)  1 39

fluazinam (XXXI) 10 56

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby’s formula (I) 1 73 + + {close oversize brace} 87 fluazinam {closeoversize brace} 1:10 10 (XXXI)

TABLE 17 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I) 1 47

compound of the formula (XXVIII)(27) 1  9

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula (I) 1 52 + {close oversize brace} 1:1 + {close oversizebrace} 72 (XXVIII) (27) 1

TABLE 18 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % compound ofthe formula (I) 1 47

compound of the formula (XIV) (13) 1  8

Mixture according to the invention: Active Expected value compoundcalculated application Actual using Colby's Mixing ratio rate in g/haefficacy formula (I) 1 51 + {close oversize brace} 1:1 + {close oversizebrace} 62 (XIV) (13) 1

TABLE 19 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % formula (I)  156

compound of the formula (XXXXVIa) (40) 50  0 copper oxychloride Mixtureaccording to the invention: Expected Active value calcu- compound latedusing application Actual Colby's Mixing ratio rate in g/ha efficacyformula formula (I) 1 56 + + {close oversize brace} 82 copperoxychloride {close oversize brace} 1:50 50 (XXXXVIa)

TABLE 20 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % formula (I) 156

compound of the formula (XII) (11) 1 55 azoxystrobin

Mixture according to the invention: Expected Active value calcu-compound lated using application Actual Colby's Mixing ratio rate ing/ha efficacy formula formula (I) 1 80 + + {close oversize brace} 95azoxystrobin (XII) {close oversize brace} 1:1 1 (XXII)

TABLE 21 Phytophthora test (tomato)/protective Active compound Effi-Active compound application cacy known: rate in g/ha in % formula (I) 156

compound of the formula (XIII) (12) 1  0 trifloxystrobin

Mixture according to the invention: Active compound Expected valueapplication Actual calculated using Mixing ratio rate in g/ha efficacyColby's formula formel (I) 1 56 + + {close oversize brace} 68trifloxystrobin {close oversize brace} 1:1 1 (XXIII)

1-6. (canceled)
 7. An active compound combination comprising at leastone compound of formula (I)

and (1) a triazole of formula (II)

in which X represents chlorine or phenyl and Y represents

and/or (2) the triazole of formula (III)

and/or (3) an aniline of formula (IV)

in which R¹ represents hydrogen or methyl, and/or (4)N-[1-(4-chloro-phenyl)-ethyl]-2,2-dichloro-1-ethyl-3-methyl-cyclopropane-carboxamideof formula (V)

and/or (5) the zinc propylene-1,2-bis-(dithiocarbamidate) of formula(VI)

and/or (6) at least one thiocarbamate of formula (VII)

in which Me represents Zn or Mn or a mixture thereof and/or (7) theaniline of formula (VIII)

and/or (8) the compound of formula (IX)

and/or (9) the benzothiadiazole of formula (X)

and/or (10) the8-t-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxaspiro[5,4]-decaneof formula (XI)

and/or (11) the cyanoxime of formula (XV)

and/or (12) a pyrimidine of formula (XVI)

in which R² represents methyl, —C≡C—CH₃ (mepanipyrim) or cyclopropyl(cyprodinyl), and/or (13) an aniline of formula (XVII)

and/or (14) the morpholine of formula (XVIII)

and/or (15) the phthalimide of formula (XIX)

and/or (16) the hydroxyethyl-triazole of formula (XXI)

and/or (17) the1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine of formula(XXII)

and/or (18) the oxazolidinedione of formula (XXIII)

and/or (19) the benzamide of formula (XXIV)

and/or (20) the guanidine of formula (XXV)

in which m represents an integer from 0 to 5 and R³ represents hydrogen(17 to 23%) or the radical of the formula

and/or (21) the triazole of formula (XXVI)

and/or (22) the halogeno-benzimidazole of formula (XXVII)

and/or (23) the tetrachloro-isophthalo-dinitrile of formula (XXIX)

and/or (24) the compound of formula (XXX)

and/or (25) the pyridineamine of formula (XXXI)

and/or (26) the thiazolecarboxamide of formula (XXXII)

and/or (27) the sulphonamide of formula (XXXIII)

and/or (28) the compound of formula (XXXIV)

and/or (29) the compound of formula (XXXV)

and/or (30) the compound of formula (XXXVI)

and/or (31) the diamide of formula (XXXVII)

and/or (32) the methoxyacrylate of formula (XXXVIII)

and/or (33) the quinoline of formula (XXXIX)

and/or (34) the phenylamide of formula (XXXX)

and/or (35) the phenylamide of formula (XXXXI)

and/or (36) the dicarboxime of formula (XXXXIIa)

and/or (37) the phosphonic acid of formula (XXXXIII)

and/or (38) the pyrrole of formula (XXXXIV)

and/or (39) the phenyl carbonate of formula (XXXXV)

and/or (40) the copper compounds (a) copper oxychloride (XXXXVIa) (b)copper hydroxide (XXXXVIb) and/or (41) the imidazole of formula(XXXXVII)

and/or (42) one or more triazoles having (a) formula (XXXXVIIIa)

and/or (b) formula (XXXXVIIIb)

and/or (c) formula (XXXXVIIIc)

and/or (d) formula (XXXXVIIId)

and/or (e) formula (XXXXVIIIe)

and/or (f) formula (XXXXVIIIf)

and/or (g) formula (XXXXVIIIg)

and/or (h) formula (XXXXVIIIh)

and/or (43) a compound of formula (XXXXIX)

in which R¹ represents unsubstituted or fluorine-, chlorine-, bromine-,methyl- or ethyl-substituted phenyl, 2-naphthyl,1,2,3,4-tetrahydronaphthyl or indanyl.
 8. The active compoundcombination according to claim 7 comprising at least one compound of theformula (I) and (1) an aniline of formula (IVb)

and/or (2) the zinc propylene-1,2-bis-(dithiocarbamidate) of formula(VI)

and/or (3) at least one thiocarbamate of formula (VIIc)

in which Me is a mixture of Zn and Mn, and/or (4) the aniline of formula(VIII)

and/or (5) the compound of formula (IX)

and/or (6) the compound of formula (XII)

and/or (7) the compound of formula (XIII)

and/or (8) the compound of formula (XIV)

and/or (9) the phthalimide of formula (XIX)

and/or (10) the hydroxyethyl-triazole of formula (XXI)

and/or (11) the halogeno-benzimidazole of formula (XXVII)

and/or (12) the halogenopyrimidine of formula (XXVIII)

and/or (13) the tetrachloro-isophthalo-dinitrile of formula (XXIX)

and/or (14) the pyridinamine of formula (XXXI)

and/or (15) the copper compounds (a) copper oxychloride (XXXXVIa) (b)copper hydroxide (XXXXVIb).
 9. The active compound combination accordingto claim 7 wherein the weight ratio of the compound of formula (I) tothe compound of formula (II) is from 1:0.1 to 1:50, the compound offormula (III) is from 1:0.1 to 1:50, the compound of formula (IV) isfrom 1:1 to 1:150, the compound of formula (V) is from 1:0.1 to 1:10,the compound of formula (VI) is from 1:1 to 1:150, the compound offormula (VII) is from 1:1 to 1:150, the compound of formula (VIII) isfrom 1:0.1 to 1:50, the compound of formula (IX) is from 1:0.1 to 1:50,the compound of formula (X) is from 1:0.02 to 1:50, the compound offormula (XI) is from 1:0.1 to 1:50, the compound of formula (XV) is from1:0.1 to 1:50, the compound of formula (XVI) is from 1:0.2 to 1:50, thecompound of formula (XVII) is from 1:0.1 to 1:50, the compound offormula (XVIII) is from 1:0.1 to 1:50, the compound of formula (XIX) isfrom 1:1 to 1:150, the compound of formula (XX) is from 1:0.1 to 1:150,the compound of formula (XXI) is from 1:0.02 to 1:50, the compound offormula (XXII) is from 1:0.05 to 1:20, the compound of formula (XXIII)is from 1:0.1 to 1:50, the compound of formula (XXIV) is from 1:0.1 to1:50, the compound of formula (XXV) is from 1:0.1 to 1:150, the compoundof formula (XXVI) is from 1:0.1 to 1:50, the compound of formula (XXVII)is from 1:0.1 to 1:50, the compound of formula (XXIX) is from 1:1 to1:150, the compound of formula (XXX) is from 1:1 to 1:150, the compoundof formula (XXXI) is from 1:0.1 to 1:50, the compound of formula (XXXII)is from 1:0.1 to 1:50, the compound of formula (XXXIII) is from 1:0.1 to1:50, the compound of formula (XXXIV) is from 1:0.1 to 1:50, thecompound of formula (XXXV) is from 1:0.1 to 1:50, the compound offormula (XXXVI) is from 1:1 to 1:50, the compound of formula (XXXVII) isfrom 1:1 to 1:150, the compound of formula (XXXVIII) is from 1:0.1 to1:50, the compound of formula (XXXIX) is from 1:0.1 to 1:50, thecompound of formula (XXXX) is from 1:0.1 to 1:50, the compound offormula (XXXXI) is from 1:0.1 to 1:50, the compound of formula (XXXXII)is from 1:1 to 1:150, the compound of formula (XXXXIII) is from 1:1 to1:150, the compound of formula (XXXXIV) is from 1:0.1 to 1:50, thecompound of formula (XXXXV) is from 1:0.1 to 1:50, the compound offormula (XXXXVIa) is from 1:1 to 1:150, the compound of formula(XXXXVIb) is from 1:1 to 1:150, the compound of formula (XXXXVII) isfrom 1:0.1 to 1:50, the compound of formula (XXXXVIIIa) is from 1:0.1 to1:50, the compound of formula (XXXXVIIIb) is from 1:0,1 to 1:50, thecompound of formula (XXXXVIIIc) is from 1:0.1 to 1:50, the compound offormula (XXXXVIIId) is from 1:0.1 to 1:50, the compound of formula(XXXXVIIIe) is from 1:0.1 to 1:50, the compound of formula (XXXXVIIIf)is from 1:0.1 to 1:50, the compound of formula (XXXXVIIIg) is from 1:0.1to 1:50, the compound of formula (XXXXVIIIh) is from 1:0.1 to 1:50, andthe compound of formula (XXXXIX) is from 1:0.1 to 1:50.
 10. An activecompound combination comprising at least one compound of formula (I)

and the tetrachloro-isophthalo-dinitrile of formula (XXIX)


11. An active compound combination according to claim 10 wherein theweight ratio of the compound of the formula (I) to the compound of theformula (XXIX) is from 1:1 to 1:150.